Monoazo dyestuffs



Patented May 13, 1941 MONOAZO DYESTUFFS Richard Fleischhauer, Frankfort-on-the-Main- Fechenheim, Carl Theo Schultis, Bergen, near Frankfort-on-the-Main, and Ernst Korten, Frankfort on the Main-Fechenheim, Germany, assignors to General Aniline & Film Corporation, a corporation of Delaware No Drawing. Application June 1, 1939, Serial No. 276,806. In GermanyJune 2, 1938 4 Claims.

Our present invention relates to valuable monoazo' dyestuffs, more particularly to those of the general formula wherein R'means a radicle of the benzene series, R1 stands for a member of the group consisting of aliphatic, hydroaromatic and aromatic radicles, R2 for a member of the group consisting of aliphatic and hydroaromatic radicles containing less than carbon atoms, R1 and R2 together containing at least 14 carbon atoms, X stands for a member of the group consisting of carbonyl (CO) and sulfoyl (S02), Y for a member of the group consisting of alkyl and aryl groups of the benzene series, said aryl group being directly linked to X by a nuclear carbon atom of the benzene nucleus, one Z stands for the. sulfonic'acid group (5031-!) and the other for hydrogen.

The new dyestuffs surpass the analogous dyestuifs as to fastness of the dyeings obtained therewith particularly to washing, fulling, sea-' wherein R1 and R2 have the aforesaid signification and reducing the nitro compounds thus formed. Among the secondary amines of this type there may be named for instance: di-isoheptylamine, di-(a-ethyl-hexyl) -amine, din-heptylamine, di-n-octylamine, di-n-nonylamine, or mixtures of such amines, N-n-butyl-laminonaphthalene, N-cyclohexyl-l-aminonapht-h a 1 en e, N-cyclohexyl-2-aminonaphthalene, N-dodekahydrodiphenyl-aniline, N-(isohexyl-cyclohexyl) -aniline, N- (isooctyl-cyclohexyl) -anil'i n e, N (isohexylphenyl) cyclohexylamine, N-ethyldodecylamine, di-hexahydrobenzylamine, N-hexahydrobenzyl-dodecylamine and the like.

The normal aliphatic secondary amines, for instance the di-n-octylamine or the di-nnonylamine are obtained in known mamier, for instance, from the corresponding alcohols which are prepared from the corresponding fatty acids by treating them with ammonia in the presence of a dehydration catalyst. The secondary isoalkylamines with a branched chain probably have'the following" constitution:

ErampZeI The diazo solution obtained from 36 parts of N- (3-amino-benzoyl) -N,N- [di-(a-ethylhexyl) amine of the formula CHzCHa /CH-CHzOH2OH2CHzCHa OO.N\

OH CHzcflzCHzcHzcHs CH2CH3' is added, while cooling, to an aqueous solution of 43 parts of 1-benzoylamino-8-hydroxynaphthalene-fi-disulfonic acid containing an excess of sodium carbonate. The dyestuff thus formed of the formula CHICHK is, when dry, a watersoluble dark red powder and dyes wool from an acid or neutral bath bright bluish red shades of a very good fastness to washing, fulling, perspiration, seawater and light.

When using as coupling component 1-(2',5'- dichlorobenzoylamino) -8- hydroxynaphthalene- 4,6-disulfonic acid or the corresponding 3,6- disulfonic acid compound, the formed dyestuifs dye bright scarlet and somewhat more bluish red shades respectively.

Example 2 The diazo solution of 34,4 parts of N-(3- amin'obenzoyl) -N-cyclohexyl-j1 -aminonaphthalene is added, While cooling, to an aqueous solution of 50 parts of l-(2',5-dichlorobenzoyl amino) 8 -hydroxynaphthalene 4,6 disulfonic acid, containing an excess of sodium carbonate.

The dyestufi thus obtained of the formula r i -Q is, when dry, a watersoluble brownish red powder and dyes wool or silk bright red shades of a good fastness to washing, fulling, perspiration, seawater and light.

When starting from N-(3-aminobenzoyl) 1 T- n-butyl-l-amino-naphthalene the formed dyestuff is a bluish red powder and dyes wool very similar shad'es.

Example 3 36 parts of a mixture of amino compounds obtained by reducing the condensation product of 4-nitr0benzoy1ch10ride and a mixture of secondary amines of the constitution are diazotized in the usual manner. The diazo solution thus obtained is added at about 5 to C. to a solution of 53 parts of 1-(2',5'-dimethyl- 5i -chlorobenzenesu1famino) -8 -hydroxynaphthalene-3,6-disulfonic acid containing an excess of sodium carbonate. The dyestuff thus obtained of the formula I 11111. s Or-QC] N 11,

E03 S S 0311 is, when dry, a watersoluble red powder and dyes wool bright yellowish red shades of similar fastness properties.

The analogous dyestuif containing in the 4-position of the benzene nucleus a methyl group dyes wool somewhat more bluish red shades.

Example 4 The diazo compound of 38,6 parts of N-(3- aminobenzoyl) N dodekahydrodiphenyl 2' methylphenylamine is combined in the presence of an excess of caustic chalk with 53 parts of 1 (2',5 dimethyl 4 chlorobenzenesulf amino) 8 -hydroxynaphthalene 3 ,6 disulfonic' acid.

The dyestuff thus formedof the formula $11:

on 1 lTH-SOzo1 N=N H3O nmssons CO H2 H5 H H2 H2 H2 H H2 H2 H H2 H2 is, when dry, a red powder and dyes wool bright red shades of good fastness properties.

Similar dyestufis are obtained by starting from 2. The monoazo dyestuff of the formula diazo compounds of amines obtained by the re- 01 duction of condensation products of 3- and 4-nitrobenzoylchloride with N- (isohexylcycloon IITELO ohexyl) phenylamine', N (isoocty1-cyc1ohexy1)'- 5 phenylamine, N (isohexylphenyl) -cyclohexyl- C1 amine, N-ethyldodecylamine, N-dodecyl-cyclo- HO S hexylamine and similar secondary amines. 3

The following table will serve to furnish further H2 H: H CO 80311 examples of dyestuffs embraced by our invention, listing the components of the said dyestufi's in Hz separate columns and indicating the shades of Hz H2 each when dyeing on wool.

Diazo-component Coupling component Shade N-(4-aminobenzoyl)-N, N-(di-isoheptyD-amine. 1-(iify-dichkgbenzoylamino) -8-hydroxynaphthalene-4, 6-di- Red.

S 01110 aci N-(3-aminobenzoyl)-N, N-(di-isoheptyD-aminm 1-3-nitgobenzoylamino)-8-hydroxynaphthalene-4,fi-disulfon- Bluish red. 10 acr N-(4-aminobenzoyD-N, N-[di-(a-ethyl-hexyb]amine l-benzoylamino-8Fhydroxynaphthalene-3, G-disulfonic acid." Do. N -(3-am1nobenz0yl) -N,N-[d1-(u-ethyl-hexyl)]-am1ne 1-(2,5-dimethyl-4 -ch1or benzenesulfoamino) 8 hydroxy- Bright bllllSh red naphtha1ene-3,6-disulfonic acid. N-(3-am1nobenzoyl)-N-(n-butyl)-1-am1no-naphthalene 1 (2,5 dimethyl 4 chlorbenzenesulfoamino) 8 hydroxy- D0.

naphthalene-3,fi-disulfonic acid. A N-(3-an11nobenzoyl)-N-cyclohexyl-1-am1nonaphthalene. 1-($85-dichlorbenzoylamino) -8-hydroxynaphthalene-4,6-d1- Red.

s ionic acid. Y y e y -am nonaphthalene 1- (2;,5-dichlorbenzoylamino)-8-hydroxynaphthalene-3,6-di- Bluish red.

su ionic acid. N-(4-aminobenzoyl)-N-cyclohexyl-l-aminonaphthalene. 1-benzoylamino-8-hydroxynaphthalene-3,fi-disulfonic acid. Do. N-(3-aminobenzoyl)-N-cyclohexyI-2-aminonaphthalene 1-(2'15-dich1orbenzoylamino)-8-hydroxynaphthalene-4,6-di- Red.

su ionic acid. N-(4-aminobenzoyl)-N-isohexyl-1-amino-naphthalene do Bluish red. N-(3-aminobenzoyl)-N-isooctyl-l-amino-naphthalene Red. N-(4-aminobenz0yl)-N-isooctyl-1-amino-naphthalene Bluish red. N (3-aminobenzoyl) -N-(dodekahydro-diphenyl)-pheny1am- ,6- Bright red.

1-acetylamin0-8-hydroxynaphthalene-3,6-disulfonic acid Do. 1-(4-methylbenzenesulfoamino) -8-hydroxynaphthalene 3,6 Blulsh red.

disulfonic acid. N-(4-am1110benzoy1)-N-(4-1sooctylphenyl)-cyclohexylamin6. 1 (2 ,5 dimethyl 4' chlorbenzenesulfoamino) 8 hydroxy- D0.

naphthalene-3,fi-disulfonic acid. D0 1-(2,5 -dichlorbenzoylamino)-8-hydr0Xynaphthalel1e-4,6-d1- Red.

sulfonic acid. N-(3-am1nobenzoyl)-N-(4-1soocty1phenyl)-cyclohexylamme 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid"... Do.

D0 l-benzoylamino-S-hydroxynaphthaleneAfi-disulfonic and... D0- Dn 1 (2,5 dichlorbenzoylamino) 8 -hydroxynaphtha1ene 3,6 13111 511 reddisulfonic acid. N-(3ammobenzoy1)-N-(4-1sohexylphenyl)-cyclohexylamine 1 (2251 dichlorbenzoylamino) 8 -hydtoxynaphtha1ene 4,6. Red.

disu fonic acid. N-(4-aminobenzoyl)-N-(4-isohexylphenyl)-cyclohexylamine 1 (2,5 dimethyl -4 chlorbenzenesulfoamino) -8 hydroxy Bluish red.

naphthalene-3,G-disulfonic acid. N-(3-am nobenzoyl)-N-dodecyl-cyclohexylamine 1-acetylamino-8-hydroxynaphthalene-4,6-disulf0n1c acid- Yellowlsh red. N-(4-am1nobenzoyl)-N-dodecyl-cyclohexylamine l-benzoylamino-S-hydroxynaphthalone-3,B-disulfonic acid Blulsh red. N- (4-amin0benzoyl) -N-dodecyl-cyclohexylamine 1 (2,5 dimethyl 4 chlorbenzenesulfoamino) 8 hydroxy- D0 naphthalene-3,fi-disulfonic acid. N- (4-am1nobenzoy1) -N-ethy1-dodecy1amine 1 (2,51 dich-lorbenzoylamino) 8 hydroxynaphthalene 3,6 D0.

disu fonic acid. N-(4-amin0benzoy1) -N-dodecylphenylamine 1 (2,5 dimethyl 4' chlorb enzcnesulfoamino) 8 hydroxy- Donaphthalene-3,G-disulfonic acid. N- (4-am1nobenzoyl) -N-(4-1sohexy1cyclohcxy1) -phenylamine 1 benzenesulfoamino 8 hydroxynaphthalene 3,6 dlsulfonlc Do. acid.

We claim:

which dyestufi is' when dry a watersoluble 1. Monoazo dyestuffs of the general formula brownish red powder and dyes animal fibers wherein R means a radicle of the benzene series, R1 stands for a member of the group consisting of aliphatic, hydroaromatic and aromatic rad-' icles, R2 for a member of the group consisting of aliphatic and hydroaromatic radicles containing less than 10 carbon atoms, R1 and R2 together containing at least 14 carbon atoms, X stands for a member of the group consisting of carbonyl (CO) and) sulfoyl (802), Y for a member of the group consisting of alkyl and aryl groups of the benzene series, said aryl group being directly linked to X by a nuclear carbon atom of the benzene nucleus, one Z stands for the sulfonic acid group (SOsH) and the other for hydrogen, which dyestufis dye the animal fibers mostly reddish shades of a good fastness particularly to washing, fulling, seawater, perspiration and light.

bright red shades of a good fastness particularly to washing, fulling, seawater, perspiration and light.

3. The monoazo dyestuif of the formula which dyestufi? is when dry a watersoluble red powder and dyes animal fibers bright bluish red shades of a good fastness particularly to washing, fulling, seawater, perspiration and light.

4. The monoazo dyestuff of the formula:

which dyestuff is, when dry, a watersoluble redpowder and dyes animal fibers bright red shades of a good fastness, particularly to washing, fulling, seawater, perspirationand. light.

RICHARD FLEISCHI-IAUER. CARL THEO SCHULTIS. ERNST KORTEN. 

